US6011180A - Acid-stable borates for photopolymerization - Google Patents

Acid-stable borates for photopolymerization Download PDF

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US6011180A
US6011180A US08/754,707 US75470796A US6011180A US 6011180 A US6011180 A US 6011180A US 75470796 A US75470796 A US 75470796A US 6011180 A US6011180 A US 6011180A
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alkyl
phenyl
substituted
halogen
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Allan Francis Cunningham
Martin Kunz
Hisatoshi Kura
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BASF Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Definitions

  • the invention relates to highly reactive borate photoinitiator compounds which are stable in acid-containing media, to photopolymerizable compositions comprising these compounds, and to the use of the compounds as initiators for polymerization.
  • R 1 is C 1 -C 20 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 8 alkenyl, phenyl-C 1 -C 6 alkyl or naphthyl-C 1 -C 3 alkyl, where the radicals C 1 -C 20 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 8 alkenyl, phenyl-C 1 -C 6 alkyl or naphthyl-C 1 -C 3 alkyl can be interrupted by one or more groups O, S(O) p or NR 5 , or where the radicals C 1 -C 20 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 8 alkenyl, phenyl-C 1 -C 6 alkyl or naphthyl-C 1 -C 3 alkyl are unsubstituted or are substituted by C 1 -C 12 alkyl, OR 6 , R
  • R 2 , R 3 and R 4 independently of one another are phenyl or biphenyl, where the radicals phenyl or biphenyl are unsubstituted or are substituted by unsubstituted or OR 6 --, NR 8 R 9 -- or halogen-substituted C 1 -C 12 alkyl, OR 6 , R 7 S(O) p , R 7 S(O) 2 O, R 8 R 9 NS(O) 2 , NR 8 R 9 , NR 8 R 9 CO, ##STR3## SiR 10 R 11 R 12 , BR 13 R 14 , halogen, R 15 R 16 P(O) q , ##STR4## wherein the sum of the Hammett ⁇ constants ( ⁇ .sub. ⁇ ) of the substitutents on the aromatic radicals R 2 , R 3 and R 4 is between +0.36 and +2.58;
  • X is O, S or NR 21 ;
  • R 5 is hydrogen, C 1 -C 12 alkyl, phenyl-C 1 -C 6 alkyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen, or phenyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen;
  • R 6 and R 7 are unsubstituted or halogen-substituted C 1 -C 12 alkyl, phenyl- C 1 -C 6 alkyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen, or phenyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 independently of one another C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, phenyl-C 1 -C 6 alkyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen, or phenyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen, or R 8 and R 9 , together with the N atom to which they are attached, form a 6-membered aliphatic ring which as a further heteroatom may additionally contain oxygen or sulfur;
  • R 17 , R 18 , R 19 and R 20 independently of one another are hydrogen, unsubstituted or C 1 -C 12 alkoxy-substituted C 1 -C 12 alkyl, phenyl or phenyl-C 1 -C 6 alkyl, where the radicals phenyl or phenyl-C 1 -C 6 alkyl are unsubstituted or are substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen;
  • p is a number from 0 to 2;
  • r is a number from 0 to 5;
  • R 21 is hydrogen or C 1 -C 12 alkyl
  • R 22 , R 22a , R 23 and R 24 independently of one another are hydrogen, unsubstituted or C 1 -C 12 alkoxy-, OH-- or halogen-substituted C 1 -C 12 alkyl or unsubstituted or C 1 -C 12 alkoxy-, OH-- or halogen-substituted phenyl;
  • q is 0 or 1
  • G is a radical which is able to form positive ions.
  • compositions comprising
  • component (b) at least one compound containing an acidic group, which acidic group may also be present in component (a);
  • the compounds of the formula I are highly reactive initiators for the photopolymerization of ethylenically unsaturated compounds, with or without the addition of coinitiators.
  • the sum of the Hammettt ⁇ constants ( ⁇ .sub. ⁇ ) of the substitutents on the aromatic radicals R 2 , R 3 and R 4 is between +0.36 and +2.58.
  • Substituted radicals phenyl or biphenyl are substituted from one to four times, for example once, twice or three times, especially once or twice.
  • C 1 -C 20 alkyl is linear or branched and is, for example, C 1 -C 12 , C 1 -C 8 , C 1 -C 6 or C 1 -C 4 alkyl.
  • it is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.
  • R 1 is C 1 -C 12 alkyl, especially C 1 -C 8 alkyl, preferably C 1 -C 6 alkyl, for example methyl or hexyl.
  • R 1 , R 2 , R 3 and R 4 are C 1 -C 20 alkyl substituted by R 9 R 10 R 11 Si
  • the alkyl radical is, for example, C 1 -C 12 alkyl, especially C 1 -C 8 alkyl, preferably C 1 -C 4 alkyl. Methyl is particularly preferred.
  • C 1 -C 12 alkyl and C 1 -C 6 alkyl are likewise linear or branched and have, for example, the definitions indicated above up to the corresponding number of C atoms.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are, for example, C 1 -C 8 alkyl, especially C 1 -C 6 alkyl, preferably C 1 -C 4 -alkyl, for example methyl or butyl.
  • C 1 -C 6 alkyl substitutents for phenyl-C 1 -C 6 alkyl, phenyl or biphenyl are, in particular, C 1 -C 4 alkyl, for example methyl or butyl. Cetyl is hexadecyl.
  • C 2 -C 20 alkyl interrupted one or more times by --O--, --S(O) p -- or --NR 5 -- is interrupted, for example, 1-9 times, for instance 1-7 times or once or twice, by --O--, --S(O) p -- oder --NR 5 --.
  • This produces, for example, structural units such as --CH 2 --O--CH 3 , --CH 2 CH 2 --O--CH 2 CH 3 , --[CH 2 CH 2 O] y --CH 3 , where y 1-9, --(CH 2 CH 2 O) 7 CH 2 CH 3 , --CH 2 --CH(CH 3 )--O--CH 2 --CH 2 CH 3 or --CH 2 --CH(CH 3 )--O--CH 2 --CH 3 .
  • C 3 -C 12 cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, especially cyclopentyl and cyclohexyl, preferably cyclohexyl.
  • C 2 -C 8 alkenyl radicals can be mono- or polyunsaturated and are, for example, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl or 7-octenyl, especially allyl.
  • R 4 as C 2 -C 8 alkenyl is, for example, C 2 -C 6 alkenyl, especially C 2 C 4 alkenyl.
  • Phenyl-C 1 -C 6 alkyl is, for example, benzyl, phenylethyl, ⁇ -methylbenzyl, phenylpentyl, phenylhexyl or ⁇ , ⁇ -dimethylbenzyl, especially benzyl. Preference is given to phenyl-C 1 -C 4 -alkyl, especially phenyl-C 1 -C 2 alkyl. Substituted phenyl-C 1 -C 6 alkyl is substituted one to four times, for example once, twice or three times, especially once or twice, on the phenyl ring.
  • Substituted phenyl is substituted one to five times, for example once, twice or three times, especially once or twice, on the phenyl ring.
  • Naphthyl-C 1 -C 3 alkyl is, for example, naphthylmethyl, naphthylethyl, naphthylpropyl or naphthyl-1-methylethyl, especially naphthylmethyl.
  • the alkyl unit can be either in position 1 or in position 2 of the naphthyl ring system.
  • Substituted naphthyl-C 1 -C 3 alkyl is substituted once to four times, for example once, twice or three times, especially once or twice, on the aromatic rings.
  • C 1 -C 12 alkoxy denotes linear or branched radicals and is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy or dodecyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, preferably methoxy.
  • Halogen is fluorine, chlorine, bromine and iodine, especially chlorine, bromine and fluorine, preferably chlorine and fluorine.
  • C 1 -C 20 alkyl is substituted one or more times by halogen, there are, for example, 1 to 3 or 1 or 2 halogen substitutents on the alkyl radical.
  • R 8 and R 9 together with the N atom to which they are attached, form a ring
  • this ring is, for example, a piperidine ring.
  • the radical is, for example, morpholino.
  • Radicals which are generally suitable as counterion G + to the negative borate in the formula I are those which are able to form positive ions.
  • alkali metals especially lithium or sodium, quaternary ammonium compounds, dye cations or cationic transition metal coordination complex compounds.
  • tetraalkylammonium is tetra(C 1 -C 4 alkyl)ammonium. This refers to compounds of the following formula: N(C 1 -C 4 alkyl) 4 + , in which C 1 -C 4 alkyl can have the definitions indicated above up to the corresponding number of C atoms.
  • appropriate ammonium compounds are tetramethylammonium, tetraethylammonium, tetrapropylammonium and tetrabutylammonium, especially tetramethylammonium and tetrabutylammonium.
  • Benzyltri(C 1 -C 4 alkyl)ammonium is also suitable. This is C 6 H 5 --CH 2 --N(C 1 -C 4 alkyl) 3 + , where C 1 -C 4 alkyl can have the definitions indicated above up to the corresponding number of C atoms.
  • Examples of such radicals are benzyltrimethylammonium, benzyltriethylammonium, benzyltripropylammonium and benzyltributylammonium, especially benzyltrimethylammonium and benyzltributylammonium.
  • trisalkylammonium ions are also suitable, for example trimethylammonium.
  • Phosphonium and ammonium counterions of the formulae + PR w R x R y R z and + NR w R x R y R z are suitable, where R w , R x , R y and R z independently of one another are hydrogen, unsubstituted or substituted alkyl, cycloalkyl, alkenyl, phenyl or arylalkyl. Examples of substitutents of these alkyl, cycloalkyl, alkenyl, phenyl and aralkyl radicals are halides, hydroxyl, heterocycloalkyl (e.g.
  • the tetravalent nitrogen may also be part of a 5- or 6-membered ring, which may in turn be fused onto other ring systems. These systems may also include additional heteroatoms, for example S, N, O.
  • the tetravalent nitrogen may also be part of a polycyclic ring system, for example azoniapropellane. These systems may also contain further heteroatoms, for example S, N, O.
  • polyammonium salts and polyphosphonium salts especially the bis salts, in which it is possible for the same substitutents to be present as described above for the "mono" compounds.
  • ammonium salts and phosphonium salts may also be substituted by neutral dyes (e.g. thioxanthenenes, thioxanthones, coumarins, ketocoumarins, etc.).
  • neutral dyes e.g. thioxanthenenes, thioxanthones, coumarins, ketocoumarins, etc.
  • Such salts are obtained by the reaction of the ammonium salts and phosphonium salts, substituted by reactive groups (e.g. epoxy, amino, hydroxyl, etc.), with appropriate derivatives of neutral dyes.
  • reactive groups e.g. epoxy, amino, hydroxyl, etc.
  • ammonium salts and phosphonium salts can also be substituted by colourless electron acceptors (e.g. benzophenones); examples of these are Quantacure ABQ ##STR5## Quantacure BPQ ##STR6## and Quantacure BTC ##STR7## from International Bio-Synthetics.
  • colourless electron acceptors e.g. benzophenones
  • quaternary ammonium compounds which are of interest are, for example, trimethylcetylammonium or cetylpyridinium compounds.
  • positive counterions G + to the borate which can be employed are further onium ions, for example iodonium or sulfonium ions.
  • counterions to the borate are radicals of the formula ##STR11## as described, for example, in EP-A 555 058 and EP-A 690 074. Also of interest as counterions are ##STR12## Further suitable counterions for the novel borates are cations of the formula ##STR13## in which R g is an alkyl radical, especially ethyl, or is benzyl, and where the aromatic ring can carry further substituents.
  • Suitable counterions are halonium ions, especially diaryliodonium ions, as described for example in EP-A 334 056 and EP-A 562 897.
  • onium cations such as ammonium, phosphonium, sulfonium, iodonium, selonium, arsonium, tellonium and bismuthonium, are described, for example, in Japanese Patent Application Hei 6 266102.
  • cationic transition metal complex compounds which are suitable as counterions are described in U.S. Pat. No. 4,954,414.
  • dyes which are suitable as counterion are cations of triarylmethanes, for example malachite green, indolines, thiazines, for example methylene blue, xanthones, thioxanthones, oxazines, acridines, cyanines, rhodamines, phenazines, for example safranin.
  • dyes containing acid groups for example methyl red, ethyl orange, methyl orange, acid yellow, rosolic acid, phenol red, fluorescein, Rose Bengal, thymolphthalein monophosphoric acid, auramine O, cresyl violet, rhodamine B, brilliant green or variamine blue.
  • the photopolymerization process to add at least one coinitiator or electron acceptor compound, (d) to the composition.
  • triarylmethanes for example malachite green
  • indolines for example thiazines, for example methylene blue
  • xanthones for example thioxanthones
  • oxazines for example acridines or phenazines, for example safranin.
  • Cationic, neutral or anionic dyes can be used as coinitiators for the novel compounds.
  • Particularly suitable cationic dyes are malachite green, methylene blue, safranin O, rhodamines of the formula III ##STR15## in which R and R' are alkyl or aryl radicals, for example rhodamine B, rhodamine 6G or violamine R, and also sulforhodamine B or sulforhodamine G.
  • Preferred cyanines are those in which Y 1 in formula IV is C(CH 3 ) 2 or S.
  • the following dye compounds are also suitable as coinitiators: ##STR18## in which Z is P, S or N and R is an alkyl or aryl radical.
  • Preferred compounds of the above formula are those in which ZR 3 is N(CH 3 ) 3 , N(C 2 H 5 ) 3 or P(C 6 H 5 ) 3 .
  • Also suitable are compounds such ##STR19## or ##STR20## as described for example by Yagci et al. in J. Polym. Sci. Part A: Polymer Chem.
  • Examples of further suitable dyes are merocyanine dyes, as described in U.S. Pat. No. 4,950,581 from column 6, line 20 to column 9, line 57.
  • coinitiators are xanthones or thioxanthones as described, for example, in U.S. Pat. No. 4,950,581, column 12, line 44 to column 13, line 15.
  • Anionic dye compounds can also be employed as coinitiators, for example.
  • Rose Bengal, eosine or fluorescein are also suitable as coinitiators.
  • Other suitable dyes for example from the triarylmethane class or azo class, are described in U.S. Pat. No. 5,143,818.
  • Examples which are likewise suitable are benzoxanthene, benzothioxanthene, pyronine or porphyrin dyes or UV absorbers. These are, for example, thioxanthone derivatives, coumarins, benzophenone, benzophenone derivatives or hexaarylbisimidazole derivatives. Examples of suitable hexaarylbisimidazole derivatives are described in U.S. Pat. Nos. 3,784,557, 4,252,887, 4,311,783, 4,459,349, 4,410,621 and 4,622,286.
  • 2-o-Chlorophenyl-substituted derivatives are particularly advantageous, for example 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bisimidazole.
  • UV absorbers suitable in this context are, for example, polycyclic aromatic hydrocarbons, for example anthracene or pyrene, and also the triazines described in EP-A-137 452, in DE-A-27 18 254 and in DE-A-22 43 621.
  • Other suitable triazines can be found in U.S. Pat. No. 4,950,581, column 14, line 60 to column 18, line 44.
  • trihalomethyltriazines for example 2,4-bis(trichloromethyl)-6-(4-styrylphenyl)-s-triazine.
  • the sum of the Hammett ⁇ constants ( ⁇ .sub. ⁇ ) of the substituents on the aromatic radicals R 2 , R 3 and R 4 of the photoinitiators of the formula I in the novel compositions must lie between +0.36 and +2.58. This means that values which are greater than +0.36 and at the same time less than +2.58 must be present. Compounds having the values +0.36 and +2.58 are inactive in substrates containing acid-forming groups.
  • ⁇ constants were proposed by Hammett in order to quantify the effect of a substituent X on the dissociation of the corresponding benzoic acid XC 6 H 4 COOH.
  • ⁇ a constant for XC 6 H 4 COOH, with X ⁇ H (that means benzoic acid), k is the constant for XC 6 H 4 COOH, and ⁇ is a reaction-specific constant for a reaction under defined conditions.
  • ⁇ has the value 1 for the dissociation of benzoic acid.
  • Hydrogen is assigned the ⁇ constant 0.00, while electron donor groups, which hinder the dissociation of a substituted benzoic acid, receive negative ⁇ constants. Electron-attracting groups, which increase the acidic strength of the substituted benzoic acid, have positive ⁇ constants.
  • the magnitude of the ⁇ constants is dependent on field effects and resonance effects of the respective susbtituent. On this subject, compare J. March, Advanced Organic Chemistry, Third Edition, McGraw-Hill Book Company, New York, 1985, page 242-250. The Hammett equation is valid for a large number of reactions under widely varying reaction conditions (Jaffe, Chem. Rev. 1953, 53, 191-261). Little et al. determined (J. Amer. Chem.
  • the values of the respective lay constants can be determined by measuring the oxidation potentials (as described by Little et al. in the articles cited above) or by determining the acidic strength of the corresponding benzoic acids.
  • R 1 is C 1 -C 20 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 8 alkenyl, phenyl-C 1 -C 6 alkyl or naphthyl-C 1 -C 3 alkyl, which radicals are unsubstituted or are substituted by C 1 -C 12 alkyl.
  • R 1 is C 1 -C 12 alkyl, allyl, cyclopentyl, cyclohexyl, benzyl or naphthylmethyl.
  • R 2 , R 3 and R 4 independently of one another are phenyl or biphenyl, which radicals are unsubstituted or are substituted by unsubstituted or OR 6 --, NR 8 R 9 -- or fluorine-substituted C 1 -C 6 alkyl or by ##STR23##
  • R 2 , R 3 and R 4 independently of one another are phenyl or biphenyl, which radicals are unsubstituted or are substituted by C 1 -C 12 alkyl, trifluoromethyl, ##STR24## OR 6 , NR 8 R 9 , halogen, BR 13 R 14 , R 7 S(O) p , R 7 S(O) 2 O or ##STR25##
  • Y 1 is C 1 -C 12 alkyl or phenyl
  • R 6 is C 1 -C 12 alkyl, trifluoromethyl, or phenyl which is substituted by C 1 -C 6 alkyl, C 1 C 12 alkoxy or halogen
  • R 7 is C 4 -C 12 tert-alkyl, trifluoromethyl, or phenyl which is substituted by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen
  • R 8 and R 9 are C 1 -C
  • G is a dye or metal complex cation, a sulfonium, sulfoxonium or iodonium cation, or G is a UV absorber compound which is able to form cations, or G is a metal cation of group I of the Periodic Table, or G is a cation MY + in which M is a metal from group II of the Periodic Table and Y is alkoxy or halogen, or G is an ammonium salt or phosphonium salt.
  • R 1 is C 1 -C 6 alkyl
  • R 2 , R 3 and R 4 are identical and are phenyl which is substituted by phenoxy
  • R 8 R 9 NS(O) 2 ##STR26## fluorine, bromine, chlorine, halogen-substituted C 1 -C 4 alkyl or ##STR27##
  • R 8 and R 9 are C 1 -C 4 alkyl;
  • R 21 is C 1 -C 4 alkyl;
  • r is the number 3; and
  • G is ammonium, trimethylammonium, tetramethylammonium, tetrabutylammonium, tetradecylammonium, trimethyl-n-cetylammonium, cetylpyridinium, methyl-2-chloropyridinium, trimethylhydroxymethylammonium, triethyl-3-bromopropylammonium, triphenylsulfonium, diphenyli
  • the compounds of the formula I can be obtained, for example, by reacting triorganoboranes (A) with organometallic reagents, for example alkyllithium compounds or Grignard reagents: ##STR29##
  • organometallic reagents for example alkyllithium compounds or Grignard reagents: ##STR29##
  • M is, for example, an alkali metal, such as Li or Na, or is MgX, where X is a halogen atom, especially Br.
  • X is halogen, especially Br, X' is halogen, alkoxy or aryloxy.
  • the definitions of the other radicals are as indicated above.
  • G in formula I above is a positive radical other than lithium or magnesium
  • these compounds can be obtained by cation exchange reactions, for example.
  • reaction conditions are generally familiar to the skilled worker.
  • an inert organic solvent for example an ether or aliphatic hydrocarbon, such as diethyl ether, tetrahydrofuran or hexane.
  • Suitable organometallic reagents for preparing the novel polyborates are, for example, the lithium compounds of the corresponding aliphatic and aromatic hydrocarbons.
  • the preparation of Grignard reagents is known to the person skilled in the art and is described in many textbooks and other publications.
  • the reaction with the organometallic reagent is expediently carried out with the exclusion of air in an inert gas atmosphere, for example under nitrogen.
  • the reaction is generally performed with cooling to 0° C. or below followed by heating to room temperature.
  • reaction mixture It is expedient to stir the reaction mixture.
  • the products are isolated and purified by methods likewise generally known to the skilled worker, for example chromatography, recrystallization, etc.
  • novel compounds of the formula I contain a dye radical as cation, they are prepared by the cation exchange reaction of an appropriate borate salt with a dye.
  • borate salts suitable for the exchange are the lithium, magnesium, sodium, ammonium or tetraalkylammonium salts.
  • novel compounds of the formula I contain a transition metal complex as cation, they can be prepared by analogy with the method described in U.S. Pat. No. 4,954,414, column 7, section 2.
  • alkyldialkoxyboranes and alkyldiaryloxyboranes can be prepared by various published procedures, for example those of Brown et al. Organometallics 1983, 2, 1316; Brown et al. Organometallics 1992, 11, 3094; Brown et al. J. Org. Chem. 1980, 2, 1316.
  • the boranes required as precursors for the novel compounds can be obtained, for example, in accordance with one of the published methods set out above.
  • the compounds of the formula I can be employed as photoinitiators for the photopolymerization of acidic compositions comprising at least one ethylenically unsaturated compound and at least one acidic group, which may also be present in the ethylenically unsaturated compound.
  • This use can also be implemented in combination with other photoinitiators, coinititators and/or other additives.
  • coinitiators or electron acceptors examples include coinitiators or electron acceptors, respectively.
  • suitable coinitiators or electron acceptors are benzopteridenediones (described in JP Hei 02 113002), substituted benzophenones (for example Michler's ketone, Quantacure ABQ, Quantacure BPQ and Quantacure BTC from International Biosynthetics), trichloromethyltriazines (described in JP Hei 01 033548), metal complexes (described in JP Hei 04 261405), porphyrins (described in JP Hei 06 202548 and JP Hei 06 195014), coumarins and ketocoumarins (described in U.S. Pat. No.
  • suitable additives are readily reducible compounds.
  • readily reducible compound in this context includes compounds as described in U.S. Pat. No. 4,950, 581, for example including iodonium salts, sulfonium salts, organic peroxides, compounds containing carbon-halide bonds (trichloromethyltriazines), heterocyclic sulfur compounds and other photoinitiators ( ⁇ -amino ketones).
  • examples of other additives are heterocyles as described in the Patents and Patent Applications U.S. Pat. No. 5,168,032, JP 02 244050, JP 02 054268, JP 01 017048 and DE 383308.
  • additives examples include aromatic imines, described in U.S. Pat. No. 5,079,126 and U.S. Pat. No. 5,200,292 (e.g. iminoquinone diazides), thiols, described in U.S. Pat. No. 4,937,159, thiols and N,N-dialkylanilines described in U.S. Pat. No. 4,874,685. It is also possible to employ two or more of the abovementioned electron acceptors and additives in combination.
  • sensitizers energy transfer compounds
  • combinations with two or more different sensitizers for example mixtures of the novel borate compounds with onium salts and thioxanthones or coumarins or dyes, are highly effective.
  • Preferred onium salts in these mixtures are diphenyliodonium hexafluorophosphate, (p-octyloxyphenyl)(phenyl)iodonium hexafluorophosphate, or corresponding other anions of these compounds, for example the halides; and also sulfonium salts, for example triarylsulfonium salts (Cyracurel® UVI 6990, Cyracurel® UVI-6974 from Union Carbide; Degacure® KI 85 from Degussa or SP-150 und SP-170 from Asahi Denka).
  • a particularly advantageous borate compound in these mixtures is tetramethylammonium hexyl-tris(m-fluorophenyl) borate.
  • the invention also provides a composition
  • a composition comprising, in addition to components (a), (b) and (c), at least one neutral, anionic or cationic dye or a thioxanthone and an onium compound.
  • a composition additionally comprising a free-radical photoinitiator, especially an a-amino ketone compound.
  • the invention provides a composition
  • a composition comprising in addition to components (a), (b) and (c) at least one compound of the formula XI ##STR32## in which R a , R b , R c and R d independently of one another are C 1 -C 12 alkyl, trimethylsilylmethyl, phenyl, another aromatic hydrocarbon, C 1 -C 6 alkylphenyl, allyl, phenyl-C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 12 cycloalkyl or saturated or unsaturated heterocyclic radicals, wherein the radicals phenyl, another aromatic hydrocarbon, phenyl-C 1 -C 6 alkyl and saturated or unsaturated heterocyclic radical are unsubstituted or substituted by unsubstituted or OR 6 --, NR 8 R 9 -- or halogen-substituted C 1 -C
  • R 6 and R 7 are unsubstituted or halogen-substituted C 1 -C 12 alkyl, phenyl-C 1 -C 6 alkyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen, or phenyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 independently of one another are C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, phenyl-C 1 -C 6 alkyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen, or phenyl which is unsubstituted or is substituted one to five times by C 1 -C 6 alkyl, C 1 -C 12 alkoxy or halogen, or R 8 and R 9 , together with the N atom to which they are attached, form a 6-membered aliphatic ring which as a further heteroatom may additionally contain oxygen or sulfur;
  • p is a number from 0 to 2;
  • q is 0 or 1
  • E is a radical which is able to form positive ions, especially alkali metals, ammonium or tetraalkylammonium.
  • the invention additionally provides a composition comprising at least one borate of the formula I and at least one dye which changes or loses its colour during or after the. irradiation, which dye may also, as cation, be part of the compound of the formula I.
  • dyes examples include cyanine dyes and pyrilium dyes.
  • the unsaturated compounds wihich are suitable as component (a) may include one or more olefinic double bonds. They may be of low (monomeric) or high (oligomeric) molecular mass.
  • monomers containing a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate and ethyl methacrylate. Silicone acrylates are also advantageous.
  • acrylonitrile acrylamide, methacrylamide, N-substituted (meth)acrylamides
  • vinyl esters such as vinyl acetate
  • vinyl ethers such as isobutyl vinyl ether, styrene , alkyl- and halostyrenes
  • N-vinylpyrrolidone vinyl chloride and vinylidene chloride.
  • Examples of monomers containing two or more double bonds are the diacrylates of ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and of bisphenol A, and 4,4'-bis(2-acryl-oyloxyethoxy)diphenylpropane, trimethyloupropane triacrylate, pentaerythritol toacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris(2-acryloyliethyl) isocyanurate.
  • polyunsaturated compounds of relatively high molecular mass examples include acrylisized epoxy resins, acrylisized polyesters, polyesters containing vinyl ether or epoxy groups, and also polyurethanes and polyethers.
  • unsaturated oligomers are unsaturated polyester resins, which are usually prepared from maleic acid, phthalic acid and one or more diols and have molecular weights of from about 500 to 3000.
  • oligomers which carry vinyl ether groups and of polymers as described in WO 90/01512.
  • copolymers of vinyl ether and maleic acid-functionalized monomers are also suitable.
  • Unsaturated oligomers of this kind can also be referred to as prepolymers.
  • esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers having ethylenically unsaturated groups in the chain or in side groups, for example unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in side chains, and also mixtures of one or more such polymers.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linolenic acid or oleic acid.
  • Acrylic and methacrylic acid are preferred.
  • Suitable polyols are aromatic and, in particular, aliphatic and cycloaliphatic polyols.
  • aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and also novolaks and resols.
  • polyepoxides are those based on the abovementioned polyols, especially the aromatic polyols, and epichiorohydrin.
  • Other suitable polyols are polymers and copolymers containing hydroxyl groups in the polymer chain or in side groups, examples being polyvinyl alcohol and copolymers thereof or polyhydroxyalkyl methacrylates or copolymers thereof. Further polyols which are suitable are oligoesters having hydroxyl end groups.
  • aliphatic and cycloaliphatic polyols are alkylenediols having preferably 2 to 12 C atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris( ⁇ -hydroxyethyl)amine, trimethylolethane, trimethylolapropane, pentaerythritol, dipentaerythritol and sorbitol.
  • the polyols may be partially or completely esterified with one or with diff erent unsaturated carboxylic acids, and in partial esters the free hydroxyl groups may be modified, for example etherified or esterified with other carboxylic acids.
  • esters are: trimethyloipropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetram ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaeryth ritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythitol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacryl ate, tripentaerythritol octalscrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaeryth
  • amides of identical or different, unsaturated carboxylic acids with aromatic, cycloaliphatic and aliphatic polyamines having preferably 2 to 6, especially 2 to 4, amino groups are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di- ⁇ -aminoethyl ether, diethylenetriamine, triethylenetetramine, di( ⁇ -aminoethoxy)- or di( ⁇ -aminopropoxy)ethane.
  • Suitable polyamines are polymers and copolymers, preferably with additional amino groups in the side chain, and oligoamides having amino end groups.
  • unsaturated amides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane, ⁇ -methacrylamidoethyl methacrylate and N[( ⁇ -hydroxyethoxy)ethyl]acrylamide.
  • Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and from diols or diamines. Some of the maleic acid can be replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, for example styrene.
  • the polyesters and polyamides may also be derived from dicarboxylic acids and from ethylenically unsaturated diols or diamines, especially from those with relatively long chains of, for example, 6 to 20 C atoms.
  • polyurethanes are those composed of saturated or unsaturated diisocyanates and of unsaturated or, respectively, saturated diols.
  • Polybutadiene and polyisoprene and copolymers thereof are known.
  • suitable comonomers are olefins, such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene or vinyl chloride.
  • Polymers with (meth)acrylate groups in the side chain are likewise known.
  • They may, for example, be reaction products of epoxy resins based on novolaks with (meth)acrylic acid, or may be homo- or copolymers of vinyl alcohol or hydroxyalkyl derivatives thereof which are esterified with (meth)acrylic acid, or may be homo- and copolymers of (meth)acrylates which are esterified with hydroxyalkyl (meth)acrylates.
  • the photopolymerizable compounds can be used alone or in any desired mixtures. It is preferred to use mixtures of polyol (meth)acrylates.
  • Compounds suitable as component (b) are those which are acids or carry an acidic group or are attached as ligand or counterion and which in the formulation adopt specific functions which are important to the ultimate properties.
  • the compounds containing acidic groups are organic or inorganic molecules to which derivatives of the abovementioned Bronsted acids are attached.
  • These may be monomers, for example acrylic acid and methacrylic acid, maleic acid and fumaric acid; phthalic acid and its anhydrides, but also unsaturated fatty acids such as linolenic acid or oleic acid.
  • oligomers and polymers containing acid groups which may be either unsaturated or saturated and may either participate in the polymerization reaction or be used as film-forming binders. These polymers and oligomers can be monosubstituted, which is often achieved by termination using an acid-containing terminating reagent, or also polysubstituted, which is achieved by copolymerization of acid-modified monomers with unmodified monomers.
  • the acid-modified oligomers and polymers are, in particular, carboxylic and sulfonic acid-modified polyesters, polyacrylates, polyamides, polyurethanes, polyols, polyethers, polyepoxides, alkyd resins, polybutadienes, polyisoprenes, polystyrenes, polyimides, cellulose, cellulose esters, chlorinated polyolefins, polyvinylbutyral, polyallyl ethers, polyvinyl ethers, polycarbonates, polyacrylonitirile, polyisocyanates, melamine resins, and the copolymers formed from the monomer building blocks of the polymers listed.
  • component (b) Other compounds containing acid groups which are suitable as component (b) are dyes such as methyl red hydrochloride, ethyl orange, methyl orange, acid yellow, rosolic acid, phenol red, fluorescein, Rose Bengal, thymolphthalein monophosphoric acid, auramine O, cresyl violet, rhodamine B, brilliant green or variamine blue.
  • Component (b) may likewise consist of pigments, fillers or other inorganic auxiliaries (for example filtration aids, antifoams, matting agents, wetting agents, agents for enhancing the scratch resistance or for improving the frictional properties, antisettling agents, emulsifiers, fungicides and biocides) which contain acid groups.
  • pigments containing acid groups are sulfonated and phosphated phthalocyanines, diketopyrrolopyrroles, for example Irgazin DPP Red BL, indanthrones, for example Irgazin Blue A3RN and quinacridones, for example Chinquasia Red Y859.
  • the fillers and auxiliaries include acidic silica gels, BaSO 4 , CaSO 4 , bleaching earths (for example Prolit, Tonsil Optimum), kieselguhr, silicic acid, kaolins, silica, bentonites, aluminium triphosphate, etc.
  • Anticorrosion agents which contain acidic groups are also suitable as component (b), possible examples being phosphate and sulfates.
  • Organic anticorrosion agents based on carboxylic acids are also employed, for example Irgacor 252.
  • Other substances which fall under the definition of component (b) are those which alter the rheological properties of the formulation, including thickeners and flow aids.
  • acidic organic polymers are employed as already described above, but branched and crosslinked polymers are also employed as thickeners.
  • Modified fillers or pigments are likewise employed for this purpose, examples including aerosils and silicic acids.
  • Binders as well can be added to these novel compositions, and this is particularly expedient when the photopolymerizable compounds are liquid or viscous substances.
  • the quantity of binder may, for example, be 5-95%, preferably 10-90% and especially 40-90% by weight relative to the overall solids content.
  • the choice of binder is made depending on the field of application and on properties required for this yield, such as the capacity for development in aqueous and organic solvent systems, adhesion to substrates and sensitivity to oxygen.
  • Suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5,000 to 2,000,000
  • the unsaturated compounds can also be used as a mixture with non-photopolymerizable, film-forming components. These may, for example, be physically drying polymers or solutions thereof in organic solvents, for instance nitrocellulose or cellulose acetobutyrate.
  • heat-curable resins examples being polyisocyanates, polyepoxides and melamine resins.
  • the use of heat-curable resins at the same time is important for use in systems known as hybrid systems, which in a first stage are photopolymerized aof thermal aftertage are crosslinked by means of thermal aftertreatment.
  • compositions in which the coinitiator (d) is a dye or a UV absorber.
  • compositions are those containing cyanine, merocyanine, anthraquinone, azo, diazo, acridine, coumarin, phenazine, phenoxazine, phenothiazine, rhodamine, xanthone, triphenylmethane or xanthene derivatives as dye.
  • compositions are those in which the dye is cresyl violet, patent blue, brilliant blue, safranin O, fluorescein, rhodamine B, pyronine G4, azure A, lissamine green, ethyl orange or methylene blue.
  • compositions are those in which the UV absorber is a thioxanthone derivative, a coumarin, benzophenone, a benzophenone derivative or a hexarylbisimidazole derivative.
  • the photopolymerizable mixtures may include various additives.
  • thermal inhibitors which are intended to prevent premature polymerization, examples being hydroquinone, hydroquinone derivatives, p-methoxyphenol, ⁇ -naphthol or sterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol.
  • copper compounds such as copper naphthenate, stearate or octanoate
  • phosphorus compounds for example triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite
  • quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, for example N-diethylhydroxylamine.
  • UV absorbers which can be added in a small quantity are UV absorbers, for example those of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type. These compounds can be used individually or in mixtures, with or without sterically hindered amines (HALS).
  • HALS sterically hindered amines
  • UV absorbers and light stabilizers examples are UV absorbers and light stabilizers.
  • 2-(2'-hydroxlvphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-
  • 2-Hydroxybenzophenones for example the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivative.
  • esters of substituted or unsubstituted benzoic acids for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example isooctyl or ethyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, methyl ⁇ -carbomethoxycinnamate, butyl or methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
  • Sterically hindered amines for example bis(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(2,2,6,6-tetramethylpiperidyl) succinate, bis(1,2,2,6,6-pentamethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6,
  • Oxalamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanalides.
  • 2-(2-Hydroxyphenyl)-1,3,5-triazines for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bi(2,4-dihydroxyphenyl)-1,3,5-triazine, 2(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin
  • Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythrityl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl diphosphite, bis-isodecyloxy pentaerythrityl diphosphite, bis(2,4-d
  • amines for example triethanolamine, N-methyldiethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone.
  • the action of the amines can be intensified by the addition of aromatic ketones of the benzophenone type.
  • amines which can be used as oxygen scavengers are substituted N,N-dialkylanilines, as are described in EP-A-339 841.
  • Other accelerators, coinitiators and autoxidizers are thiols, thioethers, disulfides or phosphines, as described in EP-A-438 123 and GB-A-2 180 358.
  • the photopolymerization can also be accelerized by adding further photosensitizers which shift or broaden the spectral sensitivity.
  • photosensitizers which shift or broaden the spectral sensitivity.
  • aromatic carbonyl compounds for example benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives and also 3-(aroylmethylene)thiazolines, but also eosine, rhodamine and erythrosine dyes.
  • the curing process can be assisted by, in particular, compositions which are pigmented (for example with titanium dioxide), and also by adding a component which under thermal conditions forms free radicals, for example an azo compound such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazo sulfide, pentazadiene or a peroxy compound, for instance a hydroperoxide or peroxycarbonate, for example t-butyl hydroperoxide, as described for example in EP-A-245 639.
  • a component which under thermal conditions forms free radicals for example an azo compound such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazo sulfide, pentazadiene or a peroxy compound, for instance a hydroperoxide or peroxycarbonate, for example t-butyl hydroperoxide, as described for example in EP-A-245 639
  • compositions comprising as component (a) at least one ethylenically unsaturated photopolymerizable compound which is emulsified or dissolved in water.
  • a prepolymer dispersion is understood as being a dispersion of water and at least one prepolymer dispersed therein.
  • the concentration of water in these systems is, for example, from 5 to 80% by weight, in particular from 30 to 60% by weight.
  • the concentration of the radiation-curable prepolymer or prepolymer mixture is, for example, from 95 to 20% by weight, in particular from 70 to 40% by weight.
  • the sum of the percentages given for water and prepolymer is in each case 100, with auxiliaries and additives being added in varying quantities depending on the intended use.
  • the radiation-curable, film-forming prepolymers which are dispersed in water and are often also dissolved are mono- or polyfunctional, ethylenically unsaturated prepolymers which are known per se for aqueous prepolymer dispersions, can be initiated by free radicals and have, for example, a content of from 0.01 to 1.0 mol of polymerizable double bonds per 100 g of prepolymer and an average molecular weight of, for example, at least 400, in particular from 500 to 10,000. Prepolymers with higher molecular weights, however, may also be considered depending on the intended application.
  • Use is made, for example, of polyesters containing polymerizable C--C double bonds and having an acid number of not more than 10, of polyethers containing polymerizable C--C double bonds, of hydroxyl-containing reaction products of a polyepoxide, containing at least two epoxide groups per molecule, with at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, of polyurethane (meth)acrylates and of acrylic copolymers which contain ⁇ , ⁇ -ethylenically unsaturated acrylic radicals, as are described in EP-A-12 339. Mixtures of these prepolymers can likewise be used.
  • polymerizable prepolymers described in EP-A-33 896 which are thioether adducts of polymerizable prepolymers having an average molecular weight of at least 600, a carboxyl group content of from 02. to 15% and a content of from 0.01 to 0.8 mol of polymerizable C--C double bonds per 100 g of prepolymer.
  • thioether adducts of polymerizable prepolymers having an average molecular weight of at least 600, a carboxyl group content of from 02. to 15% and a content of from 0.01 to 0.8 mol of polymerizable C--C double bonds per 100 g of prepolymer.
  • Other suitable aqueous dispersions, based on specific alkyl (meth)acrylate polymers, are described in EP-A-41 125, and suitable water-dispersible, radiation-curable prepolymers of urethane acrylates can be found in DE-A-29 36 039.
  • dispersion auxiliaries emulsifiers, antioxidants, light stabilizers, dyes, pigments, fillers, for example talc, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, levelling agents, lubricants, wetting agents, thickeners, matting agents, antifoams and other auxiliaries customary in paint technology.
  • Suitable dispersion auxiliaries are water-soluble organic compounds which are of high molecular mass and contain polar groups, examples being polyvinyl alcohols, polyvinylpyrrolidone and cellulose ethers.
  • Emulsifiers which can be used are nonionic emulsifiers and, if desired, ionic emulsifiers as well.
  • the quantity of photoinitiator (b) in the photopolymerizable compositions is expediently from 0.05 to 15% by weight, preferably from 0.1 to 5% by weight, based on the composition.
  • mixures of two or more of the novel photoinitiators of the formula I it may be of advantage to use mixures of two or more of the novel photoinitiators of the formula I. It is of course also possible to use mixtures with known photoinitiators, for example mixtures with benzophenone, acetophenone derivatives, for example ⁇ -hydroxycycloalkyl phenyl ketones, dialkoxyacetophenones, ⁇ -hydroxy- or ⁇ -aminoacetophenones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, monoacyl phosphine oxides, bisacylphosphine oxides or titanocenes.
  • mixtures with known photoinitiators for example mixtures with benzophenone, acetophenone derivatives, for example ⁇ -hydroxycycloalkyl phenyl ketones, dialkoxyacetophenones, ⁇ -hydroxy- or ⁇ -aminoaceto
  • Examples of particularly suitable additional photoinitiators are: 1-(4-dodecylbenzoyl)-1-hydroxy-1-methylethane, 1-(4-isopropylbenzoyl)-1-hydroxy-1-methylethane, 1-benzoyl-1-hydroxy-1-methylethane, 1-[4(2-hydroxyethoxy)-benzoyl]-1-hydroxy-1-methylethane, 1-[4(acryloyloxyethoxy)benzoyl]-1-hydroxy-1-methylethane, diphenyl ketone, penyl-1-hydroxycyclohexyl ketone, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, 1-(3,4-di-methoxyphenyl)-2-benzyl-2-dimethylamino-butan-1-one, (4-methylthiobenzoyl)-1-methyl-1-morpholinoethane, benzil dimethyl ketal, bis(cyclopentadie
  • novel photoinitiators (c) are employed in hybrid systems, use is made, in addition to the novel free-radical hardeners, of cationic photoinitiators, for example peroxide compounds, such as benzoyl peroxide (other suitable peroxides are described in U.S. Pat. No. 4,950,581 column 19, lines 17-25), aromatic sulfonium or iodonium salts (as described for example in U.S. Pat. No.
  • peroxide compounds such as benzoyl peroxide (other suitable peroxides are described in U.S. Pat. No. 4,950,581 column 19, lines 17-25), aromatic sulfonium or iodonium salts (as described for example in U.S. Pat. No.
  • compositions which in addition to the photoinitiator (c) also comprise at least one further photoinitiator (c') and/or other additives.
  • compositions comprising as additional photoinitiator (c') a titanocene, a ferrocene, a benzophenone, a benzoin alkyl ether, a benzil ketal, a 4-aroyl-1,3-dioxolane, a dialkoxyacetophenone, an ⁇ -hydroxy- or ⁇ -aminoacetophenone, an ⁇ -hydroxycycloalkyl phenyl ketone, a xanthone, a thioxanthone, an anthraquinone or a mono- or bisacylphosphine oxide, or mixtures thereof, are of particular interest.
  • additional photoinitiator (c') a titanocene, a ferrocene, a benzophenone, a benzoin alkyl ether, a benzil ketal, a 4-aroyl-1,3-dioxolane, a dialkoxyacetophenone,
  • the photopolymerizable compositions can be used for various purposes, for example as printing ink, as a clear finish, as a white finish, for example for wood or metal, as a coating material, inter alia for paper, wood, metal or plastic, as a daylight-curable coating for roadmarking and the marking of buildings, for photographic reproduction techniques, for holographic recording materials, for image recording techniques or to produce printing plates which can be developed with organic solvents or with aqueous alkalis, for producing masks for screen printing, as dental filling compositions, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etch resists or permanent resists, and as solder masks for electronic circuits, for producing three-dimensional articles by mass curing (UV curing in transparent moulds) or by the stereolithography technique, as is described, for example, in U.S.
  • novel compounds may additionally be employed as initiators for emulsion polymerizations, as polymerization initiators for fixing ordered states of liquid-crystalline monomers and oligomers, or as initiators for fixing dyes on organic materials.
  • polyunsaturated monomers which may additionally include a monounsaturated monomer as well. It is the prepolymer here which primarily dictates the properties of the coating film, and by varying it the skilled worker is able to influence the properties of the cured film.
  • the polyunsaturated monomer functions as a crosslinking agent which renders the film insoluble.
  • the monounsaturated monomer functions as a reactive diluent, which is used to reduce the viscosity without the need to employ a solvent.
  • Unsaturated polyester resins are usually used in two-component (two-pack) systems together with a monounsaturated monomer, preferably with styrene.
  • a monounsaturated monomer preferably with styrene.
  • specific one-component systems are often used, for example polymaleimides, polychalcones or polyimides, as described in DE-A-2 308 830.
  • novel compounds and mixtures thereof can also be used as free-radical photoinitiators or photoinitiating systems for radiation-curable powder coatings.
  • the powder coatings can be based on solid resins and monomers containing reactive double bonds, for example maleates, vinyl ethers, acrylates, acrylamides and mixtures thereof.
  • a free-radically UV-curable powder coating can be formulated by mixing unsaturated polyester resins with solid acrylamides (for example methyl methylacrylamidoglycolate) and a novel free-radical photoinitiator, such formulations being as described, for example, in the paper "Radiation Curing of Powder Coating", Conference Proceedings, Radtech Europe 1993 by M. Wittig and Th. Gohmann.
  • the powder coatings may also comprise binders as are described, for example, in DE-AlA 228 514 and in EP-A-636 669.
  • Free-radically UV-curable powder coatings can also be formulated by mixing unsaturated polyester resins with solid acrylates, methacrylates or vinyl ethers and with a novel photoinitiator (or photoinitiator mixture).
  • the powder coatings may also comprise binders as are described, for example, in DE-A-4 228 514 and in EP-A-636 669.
  • the UV-curable powder coatings may additionally comprise white or coloured pigments.
  • rutiletitanium dioxide can be employed in concentrations of up to 50% by weight in order to give a cured powder coating of good hiding power.
  • the procedure normally comprises electrostatic or tribostatic spraying of the powder onto the substrate, for example metal or wood, melting of the powder by heating, and, after a smooth film has formed, radiation-curing of the coating with ultraviolet and/or visible light, using for example medium-pressure mercury lamps, metal halide lamps or xenon lamps.
  • a particular advantage of the radiation-curable powder coatings over their heat-curable counterparts is that the flow time after melting the powder particles can be delayed in order to ensure the formation of a smooth, high-gloss coating.
  • radiation-curable powder coatings can be formulated to melt at lower temperatures without the unwanted effect of shortening their lifetime. For this reason, they are also suitable as coatings for heat-sensitive substrates, for example wood or plastics.
  • the powder coating formulations may also include UV absorbers. Appropriate examples are listed above in sections 1-8.
  • novel photocurable compositions are suitable, for example, as coating materials for substrates of all kinds, for example wood, textiles, paper, ceramics, glass, plastics such as polyfoters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2 to which it is intended to apply a protective layer or, by means of imagewise exposure, an image.
  • substrates of all kinds for example wood, textiles, paper, ceramics, glass, plastics such as polyfoters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2 to which it is intended to apply a protective layer or, by means of imagewise exposure, an image.
  • Coating of the substrates can be carried out by applying to the substrate a liquid composition, a solution or a suspension.
  • a liquid composition a solution or a suspension.
  • the choice of solvent and the concentration depend principally on the type of composition and on the coating technique.
  • the solvent should be inert, i.e. it should not undergo a chemical reaction with the components and should be able to be removed again, after coating, in the course of drying.
  • suitable solvents are ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate.
  • ketones such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-
  • the solution is applied uniformly to a substrate by means of known coating techniques, for example by spin coating, dip coating, knife coating, curtain coating, brushing, spraying, especially by electrostatic spraying, and reverse-roll coating, and also by means of electrophoretic deposition. It is also possible to apply the photosensitive layer to a temporary, flexible support and then to coat the final substrate, for example a copper-clad circuit board, by transferring the layer via lamination.
  • coat thickness The quantity applied (coat thickness) and the nature of the substrate (layer support) are dependent on the desired field of application.
  • the range of coat thicknesses generally comprises values from about 0.1 ⁇ m to more than 100 ⁇ m.
  • novel radiation-sensitive compositions find application as negative resists, having a very high sensitivity to light and being able to be developed in an aqueous alkaline medium. They are suitable as photoresists for electronics (electroplating resist, etch resist, solder resist), the production of printing plates, such as offset printing plates or screen printing plates, for use in chemical milling or as a microresist in the production of integrated circuits.
  • photoresists for electronics (electroplating resist, etch resist, solder resist), the production of printing plates, such as offset printing plates or screen printing plates, for use in chemical milling or as a microresist in the production of integrated circuits.
  • the possible layer supports, and the processing conditions of the coating substrates, are just as varied.
  • the compounds according to the invention also find application for the production of one- or more-layered materials for the image recording ore image reproduction (copies, reprography), which may be uni- or polychromatic. Furthermore the materials are suitable for colour proofing systems.
  • this technology formulations containing microcapsules can be applied and for the image production the radiation curing can be followed by a thermal treatment.
  • Such systems and technologies and their applications are for example disclosed in U.S. Pat. No. 5,376,459.
  • Substrates used for photographic information recording include, for example, films of polyester, cellulose acetate or polymer-coated papers; substrates for offset printing plates are specially treated aluminium, substrates for producing printed circuits are copper-clad laminates, and substrates for producing integrated circuits are silicon wafers.
  • the layer thicknesses for photographic materials and offset printing is generally from about 0.5 ⁇ m to 10 ⁇ m, while for printed circuits it is from 1 ⁇ m to about 100 ⁇ m.
  • the solvent is removed, generally by drying, to leave a coat of the photoresist on the support.
  • imagewise exposure includes both exposure through a photomask comprising a predetermined pattern, for example a slide, exposure by means of a laser beam, which for example is moved under computer control over the surface of the coated substrate and in this way produces an image, and irradiation with computer-controlled electron beams.
  • thermal treatment for a short time. In this case only the exposed sections are thermally cured.
  • the temperatures employed are generally 50-150° C., preferably 80-130° C.; the period of thermal treatment is in general between 0.25 and 10 minutes.
  • the photocurable composition may additionally be used in a process for producing printing plates or photoresists as is described, for example, in DE-A-40 13 358. In such a process the composition is exposed for a short time to visible light with a wavelength of at least 400 nm, without a mask, prior to, simultaneously with or following imagewise irradiation.
  • the unexposed areas of the photosensitive coating are removed with a developer in a manner known per se.
  • aqueous-alkaline developer solutions are aqueous solutions of tetraalkylammonium hydroxides or of alkali metal silicates, phosphates, hydroxides and carbonates. Minor quantities of wetting agents and/or organic solvents may also be added, if desired, to these solutions. Examples of typical organic solvents, which may be added to the developer liquids in small quantities, are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of such solvents.
  • Photocuring is of great importance for printing inks, since the drying time of the binder is a critical factor for the production rate of graphic products, and should be in the order of fractions of seconds. UV-curable inks are particularly important for screen printing.
  • the novel mixtures are also highly suitable for producing printing plates.
  • This application uses, for example, mixtures of soluble linear polyamides or styrene/butadiene and/or styrene/isoprene rubber, polyacrylates or polymethyl methacrylates containing carboxyl groups, polyvinyl alcohols or urethane acrylates with photopolymerizable monomers, for example acrylamides and/or methacrylamides, or acrylates and/or methacrylates, and a photoinitiator. Films and plates of these systems (wet or dry) are exposed over the negative (or positive) of the printed original, and the uncured parts are subsequently washed out using an appropriate solvent.
  • photocuring is employed is the coating of metals, in the case, for example, of the coating of metal plates and tubes, cans or bottle caps, and photocuring of polymer coatings, for example of floor or wall coverings based on PVC.
  • Examples of the photocuring of paper coatings are the colourless varnishing of labels, record sleeves and book covers.
  • the novel compounds for curing shaped articles made from composite compositions.
  • the composite composition consists of a self-supporting matrix material, for example a glass fibre fabric, or alternatively, for example, plant fibres [cf. K. P. Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370], which is impregnated with the photocuring formulation.
  • the novel compounds can also be employed as photocuring agents in moulding, impregnating and coating compositions as are described, for example, in EP-A-7086.
  • compositions are gel coat resins, which are subject to stringent requirements regarding curing activity and yellowing resistance, and fibre-reinforced mouldings, such as, for example, light diffusing panels which are planar or have lengthwise or crosswise corrugation.
  • fibre-reinforced mouldings such as, for example, light diffusing panels which are planar or have lengthwise or crosswise corrugation.
  • Techniques for producing such mouldings such as hand lay-up, spray lay-up, centrifugal casting or filament winding, are described, for example, by P.H. Selden in "Glasfaserverstarkte Kunststoffe", page 610, Springer Verlag Berlin-Heidelberg-New York 1967.
  • articles which can be produced by these techniques are boats, fibre board or chipboard panels with a double-sided coating of glass fibre-reinforced plastic, pipes, containers, etc.
  • moulding, impregnating and coating compositions are UP resin gel coats for mouldings containing glass fibres (GRP), such as corrugated sheets and paper laminates.
  • Paper laminates may be based on urea resins or melamine resins.
  • the gel coat Prior to production of the laminate, the gel coat is produced on a support (for example a film).
  • the novel photocurable compositions can also be used for casting resins or for embedding articles, for example electronic components, etc. Curing is carried out using medium-pressure mercury lamps as are conventional in UV curing. However, there is also particular interest in less intense lamps, for example of the type TL 40W/03 or TL40W/05. The intensity of these lamps corresponds approximately to that of sunlight. It is also possible to use direct sunlight for curing.
  • a further advantage is that the composite composition can be removed from the light source in a partly cured, plastic state and can be shaped, with full curing taking place subsequently.
  • compositions and compounds according to the invention can be used for the production of waveguide and optical switches wherein advantage is taken of the development of a difference in the index of refraction between irradiated and unirradiated areas.
  • photocurable compositions for imaging techniques and for the optical production of information carriers is also important.
  • Application of the photocurable layer to metal can also be carried out by electrodeposition.
  • the exposed areas are polymeric through crosslinking and are therefore insoluble and remain on the support. Appropriate colouration produces visible images.
  • the support is a metallized layer
  • the metal can, following exposure and development, be etched away at the unexposed areas or reinforced by electroplating. In this way it is possible to produce printed electronic circuits and photoresists.
  • the photosensitivity of the novel compositions extends in general from about 200 nm through the UV region into the infrared region (about 20 000 ⁇ m, in particular 1200 ⁇ m) and therefore spans a very broad range.
  • Suitable radiation is present, for example, in sunlight or light from artificial light sources. Consequently, a large number of very different types of light source are employed. Both point sources and arrays ("lamp carpets”) are suitable.
  • Examples are carbon arc lamps, xenon arc lamps, medium-, high- and low-pressure mercury lamps, possibly doped with metal halides (metal-halogen lamps), microwave-excited metal vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flashlamps, photographic floodlamps, electron beams and X-rays, produced by means of synchrotrons or laser plasma.
  • the distance between the lamp and the substrate to be exposed in accordance with the invention may vary depending on the intended application and the type and output of the lamp, and may be, for example, from 2 cm to 150 cm.
  • Laser light sources for example excimer lasers, such as krypton-F lasers for lighting at 248 nm, are especially suitable.
  • Lasers in the visible region and in the IR region can also be employed.
  • the high sensitivity of the novel materials is very advantageous.
  • the invention therefore also provides a process for the photopolymerization of nonvolatile monomeric, oligomeric or polymeric compounds containing at least one ethylenically unsaturated double bond and at least one compound which comprises an acidic group, which acidic group may also be present in the ethylenically unsaturated compound, which comprises adding to the abovementioned compounds at least one compound of the formula I according to claim 1 in which G is a dye radical or a UV-absorber, or at least one compound of the formula I according to claim 1 in combination with at least one coinitiator, and irradiating the mixture with light from the infrared region through the UV region up to a wavelength of 200 nm, and the invention also provides for the use of a composition as described above for producing pigmented and nonpigmented coating materials, powder coatings, printing inks, printing plates, adhesives, dental compositions, waveguides, optical switches, colour proofing systems, glass fibre cable coatings, screen printing stencils, resist materials, for photographical reproduction
  • the invention additionally provides a coated substrate which is coated on at least one surface with a composition as described above, and provides a process for the photographic production of relief images, in which a coated substrate is subjected to imagewise exposure and then the unexposed portions are removed with a solvent.
  • a coated substrate is subjected to imagewise exposure and then the unexposed portions are removed with a solvent.
  • a solvent is the laser beam exposure already mentioned above.
  • novel compounds of the formula I are white powders which are stable in air.
  • the sum of the Hammett a constants ( ⁇ ) of the substituents on the aromatic radicals in R 2 , R 3 and R 4 is between +0.36 and +2.58.
  • These compounds are acid-stable and can be employed in acidic photopolymerizable formulations as photohardeners.
  • novel borate compounds can be employed not only as initiators for photopolymerization reactions but also as thermal polymerization initiators. Consequently, the invention also provides for the use of the compounds of formula I as initiators for the thermal polymerization of compounds containing ethylenically unsaturated double bonds, and a process for the thermal polymerization of compounds containing ethylenically unsaturated double bonds, which comprises employing at least one compound of the formula I as polymerization initiator.
  • alkyl radicals having more than three C atoms are referred to without any mention of specific isomers, the n-isomers are meant in each case.
  • Tetramethylammonium butyl tris(2,6-difluorophenyl) borate 1.0 equivalent of butyllithium (0.012 mol) in hexane is added at 0° C. to a solution of 5.0 g (0.012 mol) of tris(2,6-difluorophenyl)borane in 20 ml of tetrahydrofuran (THF) at a rate such that the temperature does not exceed 5° C.
  • THF tetrahydrofuran
  • the reaction mixture is allowed to warm to room temperature and is stirred for 0.5 h.
  • the mixture is subsequently concentrated in vacuo and the oily residue is dissolved in 80 ml of a 4:1 mixture of methanol and water.
  • Tetramethylammonium hexyl tris(p-chlorophenyl) borate A small portion of a solution of 5.8 g (0.03 mol) of 1-bromo-4-chlorobenzene in 30 ml of THF is added to a suspension of 0.73 g (0.03 mol) of magnesium turnings in 10 ml of THF. The reaction mixture is heated until the Grignard reaction begins. When the reaction begins, heating is discontinued and the rest of the 1-bromo-4-chlorobenzene solution is added dropwise over the course of 20 minutes so as to retain a gentle reflux. Following the addition, heating is resumed until the remaining magnesium has been consumed.
  • the borate compounds of Examples 4-27 are prepared in analogy to the Methods A, B or C described in Examples 1-3, using the corresponding boranes.
  • the structures and physical data of the compounds are given in Table 1 below.
  • Photocuring of an acrylate mixture A photocurable composition is prepared from
  • the mixture is stirred at room temperature for 1-2 hours in order to dissolve the photoinitiator. All operations are carried out under red light.
  • the samples to which initiator has been added are applied to 300 ⁇ m aluminium foil (10 ⁇ 15 cm).
  • the solvent is removed by drying at room temperature for 5 minutes and then heating at 60° C. in a convection oven for 15 minutes. Over the liquid film there is placed a 76 ⁇ m thick polyester film, on which is laid a standardized test negative with 21 steps of different optical density (Stouffer wedge).
  • a second polyester film is applied over this assembly, and the resulting laminate is fixed on a metal plate.
  • the sample is then exposed for 40 seconds using a 4 kW xenon lamp at a distance of 30 cm.
  • the cover films and the mask are removed, and the exposed film is developed with 0.85% strength aqueous sodium carbonate solution in an ultrasound bath and then dried at 40° C. in a convection oven for 5 minutes.
  • the sensitivity of the initiator system used is characterized by indicating the last wedge step reproduced without tack. The higher the number of steps, the more sensitive the system. On this scale, an increase by two steps denotes approximately a doubling of the curing rate.
  • Tables 2a-2c The results are reproduced in Tables 2a-2c.
  • Example 46 The procedure of Example 46 is repeated but using 0.3% of the compound from Example 6, containing the QTX radical as cation, instead of a mixture of 0.4% of borate compound and 0.3% of Quantacure QTX.
  • the number of steps cured is 10.
  • Example 46 The procedure of Example 46 is repeated but using 0.3% of the compound from Example 7, containing a cyanine radical as cation, instead of a mixture of 0.4% of borate compound and 0.3% of Quantacure QTX. The number of steps cured is 12.
  • Example 46 The procedure of Example 46 is repeated but using 0.4% of the compound from Example 5 and 0.3% of a dye instead of a mixture of 0.4% of borate compound and 0.3% of Quantacure QTX.
  • the dyes used and results obtained are listed in Tables 3 to 3c.
  • a photocurable composition is prepared by mixing the following components:
  • Portions of this composition are mixed with in each case 0.8% of the compound from Example 5 and 0.6% of a dye, based on the solids content. All operations are carried out under red light.
  • the samples to which initiator has been added are applied in a dry-film thickness of 35 ⁇ m to a 200 mm aluminium foil (10 ⁇ 15 cm). The solvent is removed by heating at 60° C. in a convection oven for 15 minutes. Onto the liquid film there is placed a 76 ⁇ m thick polyester film, over which a standardized test negative with 21 steps of different optical density (Stouffer wedge) is applied.
  • the sample is covered with a second UV-transparent film and is pressed on a metal plate by means of vacuum.
  • the sample is then exposed for 40 seconds using a MO61/5 kW lamp at a distance of 30 cm. Following exposure, the cover films and the mask are removed and the exposed film is developed with 0.85% strength aqueous sodium carbonate solution in an ultrasound bath for 240 seconds and is then dried at 60° C. in a convection oven for 15 minutes.
  • the sensitivity of the initiator system used is characterized by indicating the last wedge step reproduced without tack. The higher the number of steps, the more sensitive the system. The results are given in Tables 4 and 4a.
  • Portions of this composition are mixed with 0.6% of the compound from Example 5, and 0.4% of isopropylthioxanthone, 0.8% of diphenyliodonium hexafluorophosphate, based on the solids content. All operations are carried out under red light.
  • the samples to which initiator has been added are applied in a dry-film thickness of 35 ⁇ m to a 200 mm aluminium foil (10 ⁇ 15 cm). The solvent is removed by heating at 60° C. in a convection oven for 15 minutes. Onto the liquid film there is placed a 76 ⁇ m thick polyester film, over which a standardized test negative with 21 steps of different optical density (Stouffer wedge) is applied.
  • the sample is covered with a second UV-transparent film and is pressed on a metal plate by means of vacuum.
  • the sample is then exposed for 10, 20 or 40 seconds using an SMX-3000 metal halide-doped high-pressure mercury lamp at a distance of 30 cm.
  • the cover films and the mask are removed and the exposed film is developed with 1% strength aqueous sodium carbonate solution in an ultrasound bath for 180 seconds at 30° C. and is then dried at 60° C. in a convection oven for 15 minutes.
  • the sensitivity of the initiator system used is characterized by indicating the last wedge step reproduced without tack. The higher the number of steps, the more sensitive the system. The results are given in Table
  • a photocurable composition is prepared by mixing the following components:
  • a photocurable composition is prepared by mixing the following components:
  • Example 46 The procedure of Example 46 is repeated but using 0.4% of the compound from Example 20, containing the 2,3,6-triphenylpyrylium as cation, instead of a mixture of 0.4% of borate compound and 0.3% of Quantacure QTX. The number of steps cured is 13. Bleaching out of the film was observed.
  • Example 46 The procedure of Example 46 is repeated but using 0.4% of the compound from Example 21, containing the methylene blue as cation, instead of a mixture of 0.4% of borate compound and 0.3% of Quantacure QTX. The number of steps cured is 15. Bleaching out of the film was observed.
  • Example 46 The procedure of Example 46 is repeated but using 0.4% of the compound from Example 22 containing the safranin O as cation, instead of a mixture of 0.4% of borate compound and 0.3% of Quantacure QTX. The number of steps cured is 17. Bleaching out of the film was observed.
  • Example 46 The procedure of Example 46 is repeated but using a mixture of 0.4% of borate compound and 0.3% of safranin O. The results are reproduced in Table 8.
  • Example 46 The procedure of Example 46 is repeated but using a mixture of 0.4% of the compound from Example 5 and 0.3% of dye.
  • the xenon lamp is replaced by a frequency-doubled Nd/YAG laser (COHERENT DPSS 532-50, beam diameter 0.7 mm, divergence ⁇ 1.3 mrad) with monochromatic light of wavelength 532 nm and with an output of 50 mW.
  • the laser beam with a diameter of about 3.3 mm, is moved at a rate of 6 mm/s over a 21-step Stouffer wedge fixed to the sample. Development leaves a line varying in width and length. For evaluation, a statement is made of the number of steps at which a cured line can still be seen.
  • the dyes used and results obtained are listed in Table
  • a photocurable formulation is prepared by mixing the following components:
  • Portions of this composition are mixed with 0.4%, based on the total quantity of the formulation, of the compound 5 and 0.3% of a dye. All operations are carried out under red light.
  • the formulations are applied to a 300 ⁇ m aluminium foil. The thickness of the dry film is 60 ⁇ m. To this film there is applied a 76 mm thick polyester film. Exposure is carried out using a frequency-doubled NdlNYAG laser (COHERENT DPSS 532-50, beam diameter 0.7 mm, divergance ⁇ 1.3 mrad) with monochromatic light of wavelength 532 nm and with an output of 50 mW.
  • COHERENT DPSS 532-50 beam diameter 0.7 mm, divergance ⁇ 1.3 mrad
  • the laser beam with a diameter of about 3.3 mm, is moved at a rate of 6 mm/s over a 21-step Stouffer wedge fixed to the sample.
  • the cover films and the mask are removed and the exposed film is developed in ethanol in an ultrasound bath at 23° C. for 10 seconds. Drying is carried out at 40° C. in a convection oven for 5 minutes. Development leaves a line varying in width and length. For evaluation, a statement is made of the number of steps at which a cured line can still be seen.
  • the dyes used and results obtained are given in Table
  • Example 57 The same formulations as in Example 57 are used, and portions of this composition are mixed with 0.4%, based on the total quantity of the formulation, of the compound 5 and 0.3% of a dye. All operations are carried out under red light.
  • the samples are placed in pill bottles with a diameter of about 3 cm.
  • These formulations, in the bottles, are exposed using a frequency-doubled Nd/YAG laser (COHERENT DPSS 532-50, beam diameter 0.7 mm, divergence ⁇ 1.3 mrad) with monochromatic light of wavelength 532 nm and with an output of 50 mW for 10 seconds at a distance of 30 cm.
  • COHERENT DPSS 532-50 beam diameter 0.7 mm, divergence ⁇ 1.3 mrad
  • monochromatic light of wavelength 532 nm
  • the uncured formulation is poured out and the remaining, cured layer is developed in ethanol in an ultrasound bath at 23° C. for 10 seconds.
  • Example 50 The procedure of Example 50 is repeated but using 0.4% of the dye-borate salts. Moreover, the xenon lamp is replaced by a frequency-doubled Nd/YAG laser (COHERENT DPSS 532-100, beam diameter 0.7 mm, divergence ⁇ 1.3 mrad) with monochromatic light of wavelength 532 nm and with an output of 100 mW.
  • the laser beam with a diameter of about 3.3 mm, is moved at a rate of 6 mm/s over a 21-step Stouffer wedge fixed to the sample. Development leaves a line varying in width and length. For evaluation, a statement is made of the number of steps at which a cured line can still be seen.
  • the dyes used and results obtained are listed in Table
  • Example 60 The procedure of Example 60 is repeated but using dye-borate salts in concentrations such that the optical density of a 2 mm film for the wavelength 532 nm is 0.5, and compound 5 is additionally used.
  • Deviating from Example 61 use is made of a frequency-doubled Nd/YAG laser (COHERENT DPSS 532-100, beam diameter 0.7 mm, divergence ⁇ 1.3 mrad) with monochromatic light of wavelength 532 nm and with an output of 100 mW, and exposure is carried out for 5 seconds at a distance of 30 cm.
  • COHERENT DPSS 532-100 a frequency-doubled Nd/YAG laser
  • Example 59 The same formulations as in Example 59 are used, and portions of this composition are mixed with 0.4%, based on the total quantity of the formulation, of the compound 5 and 0.3% of a dye. All operations are carried out under red light.
  • the samples are placed in black plastic lids with a diameter of about 1.5 cm and a height of about 12 mm and are covered wtih a Mylar film. These samples are exposed using daylight and a dose of 1200 mJ/cm 2 .
  • the uncured formulation is poured out and the cured film which remains is developed in ethanol in an ultrasound bath at 23° C. for 1 minute. Drying takes place at 40° C. in a convection oven for 5 minutes.
  • the thickness of the cured layer is measured, which is a measure of the capacity for through-curing.
  • the dyes used and results obtained are reproduced in Table
  • Example 63 The procedure of Example 63 is repeated but using, instead of mixtures of borates and dyes, 0.4% of the novel dye-borate salts and a dose of only 200 mJ/cm 2 .
  • the results are reproduced in Table
  • Example 46 The procedure of Example 46 is repeated but adding in each case 1.7% of a free-radical photoinitiator together with 0.4% of the compound 5 and 0.3% of Quantacure ITX. For exposure, however, an iron-doped mercury lamp is used for 40 seconds at a distance of 30 cm. The results are described in Table
  • Example 46 The procedure of Example 46 is repeated but adding in each case 0.1% of a cationic photoinitiator together with 0.4% of compound 5. The results are described in Table
  • Example 46 The procedure of Example 46 is repeated but adding in each case 0.4% of a cationic photoinitiator together with 0.4% of the compound 5 and 0.3% of a dye. The results are described in Table

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